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CN101589083A - Cosolvent free self-crosslinking polyurethane dispersions - Google Patents

Cosolvent free self-crosslinking polyurethane dispersions Download PDF

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Publication number
CN101589083A
CN101589083A CNA200780046865XA CN200780046865A CN101589083A CN 101589083 A CN101589083 A CN 101589083A CN A200780046865X A CNA200780046865X A CN A200780046865XA CN 200780046865 A CN200780046865 A CN 200780046865A CN 101589083 A CN101589083 A CN 101589083A
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CN
China
Prior art keywords
mixture
self
crosslinking
urethane
acid
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Granted
Application number
CNA200780046865XA
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Chinese (zh)
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CN101589083B (en
Inventor
S·多尔
H·米勒
T·赫贝斯特赖特
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Covestro Deutschland AG
Bayer Intellectual Property GmbH
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Bayer MaterialScience AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Lubricants (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The present invention relates to a process for the preparation of self-crosslinking polyurethane dispersions, to self-crosslinking aqueous dispersions obtainable by this process, to their use as coating agents, to coating agents comprising the self-crosslinking aqueous dispersions, to a process for coating substrates, and to substrates treated with coating agents comprising the self-crosslinking aqueous dispersions.

Description

The self-crosslinkable polyurethane dispersions that does not contain solubility promoter
Technical field
The present invention relates to be used to prepare self-crosslinkable polyurethane dispersions method, can self-crosslinking obtained by this method aqueous dispersion, they as the purposes that applies agent (Beschichtungsmittel), comprise the aqueous dispersion of described self-crosslinking the coating agent, be used for the method for coated substrate and with the coating agent treated base material of the aqueous dispersion that comprises described self-crosslinking.
Background technology
Discovered in recent years, owing to the release regulation that applies the solvent in the process about paint vehicle is more and more stricter, the continuous increase of the importance of water-based paint vehicle and coating agent.Although there has been at present water-based paint vehicle system at many Application Areass, these systems still usually significant quantity usually from preparation technology's solubility promoter.Especially, still openly do not have so far low solubility promoter content from containing the coating agent based on urethane of water preparation, and fully satisfy the prime strict demand of (Automobilerstlackierung) practice of automobile.
Realizing further improvement aspect single component (1K) baking finish in recent years.Application EP-A1311571 has put down in writing self-crosslinkable polyurethane dispersions, it derives from the polyvalent alcohol that contains carbamate groups and oh group and the physical mixture of non-hydrophilic polyisocyanate, described non-hydrophilic polyisocyanate with dimethyl pyrazole oxazole derivatives end-blocking at least 50% normal degree.These polyol components and from the aspect of coating, have significant advantage through the physical mixture of end capped polyisocyanates, but with regard to its preparation, have significant disadvantage.On the one hand,, describedly in the reaction vessel that end capped polyisocyanate component is separating, prepare, compare with the method for in a container, carrying out and this means significantly more and pay in described application.On the other hand, because this remarkable viscosity through end capped polyisocyanates, regulation must be added solvent in pure substance, and this is because otherwise can't measure interpolation.Based on safety factors, this class solution in high volatile volatile solvent (for example acetone), such as, can not be stored or be transported, the result has only the solvent of low volatility to can be used for through end capped polyisocyanates.These solvents remain in dispersion and the paint vehicle preparation inevitably, and only discharge in user's place, and this is normally undesirable.The self-crosslinking baking system that is recorded among the EP-A 1311571 record contains the solubility promoter with respect to dispersion 4.8 weight %-11.3 weight %, and this is to some water base application system Application Areas and Yan Taigao.
Another shortcoming of the method for record is among the EP-A 1 311 571, can not inevitable stably be dissolved in the solvent through end capped polyisocyanates.Thereby can not use some end-capping reagent.
Summary of the invention
Therefore, the object of the present invention is to provide the moisture polyisocyanic acid ester dispersion of self-crosslinking, it does not contain solubility promoter or only contains indivisible solubility promoter, thereby the evaporation of solubility promoter can not take place in end user's place.
This target realizes that by means of the method for the aqueous polyurethane dispersion that is used to prepare self-crosslinking this method comprises the steps:
I. allow a1) polyisocyanates and a2) and mixture a3) react,
A2) contain the anionic hydrophilic reagent (Hydrophilierungsmittel) of the average OH functionality of at least one isocyanate-reactive (isocyanatreaktive) group and having 〉=1,
A3) have＞at least a polyol component of 1 average OH functionality,
A2 wherein) and mixture a3) or component a1) comprise
K) at least a catalyzer;
II. obtain OH functional (OH-funktionell), do not contain the urethane of NCO group from step I, this urethane subsequently with
III.a4) the reactive end-capping reagent at isocyanate groups mixes;
This mixture that IV. will derive from Step II I subsequently with
A5) one or more are selected from a1) polyisocyanates reaction, these polyisocyanates and a1) identical or different, then
V. from step IV obtain that OH is functional, the urethane that do not contain the NCO group and end-blocking the physical mixture of polyisocyanates, wherein, afterwards or
VI. by adding
A6) neutralization reagent
Acidic group to the functional urethane of OH carries out deprotonation wholly or in part;
The urethane that VII. also will derive from this step VI is scattered in the water
Step VII carries out before step VI.
The method according to this invention advantageously, step VI carries out before step VII.
The method according to this invention advantageously, step VII carries out before step VI.
The method according to this invention advantageously, the end-capping reagent that uses among the Step II I is the compound that is selected from Diacetylmonoxime, diisopropylamine and 3.
The method according to this invention advantageously, to derive from the urethane of Step II, use after Step II or Step II I at the most that 30 weight % are selected from the solvent or the solvent mixture of acetone, methyl ethyl ketone and tetrahydrofuran (THF) and their mixture, and after step VII, remove subsequently by distillation.
The present invention further provides the aqueous polyurethane dispersion of the self-crosslinking that can make by method of the present invention.
The aqueous polyurethane dispersion that the present invention further provides self-crosslinking is used to prepare the purposes that applies agent.
The present invention further provides the coating agent, it comprises the aqueous polyurethane dispersion of self-crosslinking of the present invention.
For coating agent of the present invention advantageously, they are selected from colorant (Farbe), paint vehicle and tackiness agent.
The present invention further provides the method that is used for coated substrate, wherein use coating agent of the present invention.
The method according to this invention is advantageously used the parts of coating agent applying machine motor-vehicle bodies of the present invention or motor vehicle body.
The present invention further provides base material, it comprises coating, and described coating comprises coating agent of the present invention.
For goods of the present invention advantageously, it is the parts of whole motor vehicle body or motor vehicle body.
Embodiment
In dispersion of the present invention, handy a4) end-blocking isocyanate groups be 0.2-5.0 with the ratio that isocyanic ester is reactive OH group: 1, be preferably 0.4-2.0: 1,0.5-1.5 more preferably: 1.
Like this amount of each component of weighing, so that obtain the component a1 of following weight ratio)-a6):
A1): the 3-25 weight part, be preferably the 6-18 weight part, be preferably the 7-14 weight part especially;
A2): the 0.3-8 weight part, be preferably the 1-6 weight part, be preferably the 2-5 weight part especially;
A3): the 40-85 weight part, be preferably the 50-75 weight part, be preferably the 60-70 weight part especially;
A4): the 1-20 weight part, be preferably the 3-17 weight part, be preferably the 4-10 weight part especially;
A5): the 3-25 weight part, be preferably the 5-20 weight part, be preferably the 9-17 weight part especially;
A6): the 0.5-10 weight part, be preferably the 1-6 weight part, be preferably the 2-4 weight part especially;
K): the 0.001-2 weight part, be preferably the 0.005-0.1 weight part, be preferably the 0.01-0.08 weight part especially;
Described weight part refers to the component of defined, and does not comprise the solvent that water maybe may exist.
Used neutralization reagent a6) amount is so weighed usually, make and to be present in hydroxy-acid group in the urethane that derives from Step II and/or the degree of neutralization (mol ratio of the used amine and the acidic group of existence) of sulfonic acid group is at least 50%, preferred 80%-120%, preferred especially 95%-105%.This neutralization can before dispersion steps VII or the dissolving step, during or carry out afterwards.But be preferably neutralization (before the step VII) before adding water.
At component a1) in, can use all to contain the organic compound of isocyanate groups, but preferably have the aliphatic series of NCO functionality 〉=2, alicyclic, aromatics or heterocycle polyisocyanates, use separately or with any desired mutual mixture, no matter they are by phosgenation or by the method preparation that does not contain phosgene.
The example of this kind isocyanate is a tetramethylene diisocyanate, hexanaphthene-1,3-and-1, the 4-vulcabond, hexamethylene diisocyanate (HDI), 1-isocyanato--3,3,5-trimethylammonium-5-isocyanato-methylcyclohexane (isophorone diisocyanate, IPDI), methylene-bis (4-isocyanato-hexanaphthene), tetramethylxylylene diisocyanate (TMXDI), three isocyanato-nonanes, tolylene diisocyanate (TDI), ditan-2,4-and/or-4,4 '-vulcabond (MDI), triphenyl methane 4,4 '-vulcabond or naphthalene-1, any mixture of 5-vulcabond and this kind isocyanate.
Similarly; fit closely is derived from polyisocyanates above-mentioned and that have uretdione, carbodiimide, isocyanuric acid ester, iminooxadiazinedionepolyisocyanates diketone, biuret, carbamate, allophanate, oxadiazine triketone or acylurea structure; and have＞polyisocyanate prepolymers of 1 average N CO functionality, this class polyisocyanate prepolymers for example pre-reaction carried out of the organic substance of a kind of above-mentioned polyisocyanates and the per molecule by molar excess with at least two isocyanate reactive hydrogen atoms (for example OH group form) makes.
At a1) in, the compound with 140-1000g/mol molecular weight of aforesaid kind preferably used.
Particularly preferably in component a1) in the use polyisocyanates or the polyisocyanate mixtures that exclusively contain aliphatic series or the isocyanate groups that connects of alicyclic mode of having stated kind, particularly based on hexamethylene diisocyanate (HDI), those of isophorone diisocyanate (IPDI) and/or 4,4 '-two isocyanato-dicyclohexyl methyl hydrides.
Described polyol component a2) preferably has 1-6, the more preferably average OH functionality of 2-4, number-average molecular weight with 62-2500g/mol, be preferably 62-1000g/mol, 62-500g/mol more preferably, and containing acid-functionalized compound, it also contains at least one isocyanate-reactive OH group except sour official's energy.
These compounds be preferably contain at least one, the carboxylic acid of preferred one or 2 hydroxyl, or the salt of this class hydroxycarboxylic acid.This suitable class acid is, for example: 2, two (methylol) alkane carboxylic acids of 2-, such as dihydroxymethyl acetate, 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid or 2,2-dihydroxymethyl valeric acid, dihydroxysuccinic acid, hydroxy new pentane acid or these sour mixtures.
As component a5), preferably use dimethylol propionic acid and/or hydroxy new pentane acid.
Preferred especially a2) exclusively contains this aforesaid acid-functionalized compound, and very particularly preferably exclusively use dimethylol propionic acid) as a2.
At a3) in the polyol component that uses form by following:
B1) dibasic alcohol is to hexavalent alcohol, and the number-average molecular weight that it has 62-300g/mol is preferably 62-182g/mol, is preferably 62-118g/mol especially,
B2) polyvalent alcohol, it has 〉=2 OH functionality, and have the number-average molecular weight of 300-5000g/mol, and be preferably 300-3000g/mol, be preferably 300-2000g/mol especially, and/or
B3) simple function line style polyethers, the number-average molecular weight that it has 300-3000g/mol is preferably 300-2000g/mol, is preferably 300-1000g/mol especially.
Suitable polyvalent alcohol b1) be dibasic alcohol to hexavalent alcohol and/or their mixture, it does not contain ester group.Typical example is a 1,1, and 2-propylene glycol and 1, ammediol, 1,4-butyleneglycol, 1,2-butyleneglycol or 2,3-butyleneglycol, 1,6-hexylene glycol, 1,4-dihydroxyl hexanaphthene, glycerine, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane and Sorbitol Powder.
To b1), preferred compound is 1,4-butyleneglycol or 1,3 butylene glycol, 1,6-hexylene glycol and/or TriMethylolPropane(TMP).
Components b 2) suitable polyvalent alcohol is selected from polyethers, polyester and/or polycarbonate.Preferred b2) comprise at least a polyvalent alcohol, this polyvalent alcohol contains ester group and has the number-average molecular weight of 350-4000g/mol, is preferably 350-2000g/mol, is preferably 350-1000g/mol especially.Preferred average OH functionality is a per molecule 2-4 OH group.
This polyvalent alcohol that contains ester group is known polyester polyol itself, and it is synthetic by low-molecular-weight polyvalent alcohol and dicarboxylic acid.The example that is used for the suitable low molecular weight polyols of this purpose is 1,4-butyleneglycol, 1,3 butylene glycol, 1,6-hexylene glycol, 2,2,4-trimethylammonium-1,3-pentanediol, TriMethylolPropane(TMP), tetramethylolmethane or Sorbitol Powder.The example of suitable dicarboxylic acid is for example phthalic acid, m-phthalic acid and a terephthalic acid of aromatic dicarboxylic acid; The cycloaliphatic dicarboxylic acid is hexahydrophthalic acid, tetrahydrophthalic acid, interior methylene radical tetrahydrophthalic acid and/or their acid anhydrides for example; With aliphatic dicarboxylic acid for example succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid and/or their acid anhydrides.Aliphatic dicarboxylic acid is preferred for synthetic esterdiol.
As components b 2) in polyester polyol, it preferably uses polycaprolactone glycol, the number-average molecular weight that it has 350-4000g/mol is preferably 350-2000g/mol, is preferably 350-1000g/mol especially.These glycol can make as initiator and 6-caprolactone from above glycol, triol or glycol/three alcohol mixtures of enumerating kind by currently known methods.
Preferred polycaprolactone glycol is by using 1, and the 6-hexylene glycol prepares as initiator polymerization 6-caprolactone.
Particularly preferred polyester polyol is based on following those: with hexanodioic acid, phthalic acid, m-phthalic acid and terephthalic acid as acid constituents; With with 1,4-butyleneglycol or 1,3 butylene glycol, 1,6-hexylene glycol and/or TriMethylolPropane(TMP) are as alkoxide component.
In components b 2) in, (being total to) polyethers of propylene oxide (Ethylenoxid), propylene oxide (Propylenoxid) and/or tetrahydrofuran (THF) also can be used.Preferred polyethers is the polyethers with 500-2000g/mol number-average molecular weight, for example polyethylene oxide or polytetrahydrofuran diol.
This external b2) in, also can comprise the polycarbonate of hydroxyl, for example hexylene glycol polycarbonate or polyestercarbonate have preferred number-average molecular weight 400-4000g/mol, preferred especially 400-2000g/mol.
Components b 3) suitable simple function line style polyethers is, for example: (being total to) polyethers of oxyethane and/or propylene oxide.Preferably from the initial polyalkylene oxide polyethers of monohydroxy-alcohol, it has number-average molecular weight 350-2500g/mol, has at least 70% ethylene oxide unit.Particularly preferred this (being total to) polymkeric substance has ethylene oxide unit and the number-average molecular weight 300-2500g/mol greater than 75%, is preferably 500-1000g/mol.The starter molecules of using in these polyethers of preparation is preferably the monofunctional alcohol with 1-6 carbon atom.
A4) end-capping reagent that uses in is selected from the own known end-capping reagent that is used for isocyanate groups; The reactivity of employed end-capping reagent and isocyanate groups must be than the OH group of polyether polyols with reduced unsaturation higher.The example of suitable end-capping reagent is a for example Diacetylmonoxime of oxime, and amine is diisopropylamine for example, or tert-butyl benzyl amine, 3, triazole or their mixture.Be preferably Diacetylmonoxime, diisopropylamine, 3 or their mixture.
The reactivity of described end-capping reagent and isocyanate groups is easily measured by those skilled in the art and based on 0-100 ℃ temperature range, is preferably 20-60 ℃.This reactivity can strengthen by well known to a person skilled in the art catalyzer; By such catalyzer, also can have at ground to make the reactivity enhancing De Genggao of the reactivity of end-capping reagent than the alcohol groups of polyvalent alcohol.
As a5) polyisocyanate component can be by component a1) down listed same unit form.This component a1) and a5) can be identical or different.
For a5), the isocyanate functionality that preferred polyisocyanate component and/or its mixture have the 2-6 scope, 2.5-5 more preferably, and the most special 3-4.5 that is preferably.
As a6) the example of neutralization reagent be triethylamine, dimethylaminoethanol, dimethylcyclohexylam,ne, trolamine, methyldiethanolamine, diisopropanolamine (DIPA), ethyl diisopropyl amine, di-isopropyl cyclo-hexylamine, N-methylmorpholine, 2-amino-2-methyl-1-propanol, ammonia, oxyhydroxide be sodium hydroxide or their any mixture for example.Preferred neutralization reagent is a for example triethylamine of tertiary amine, di-isopropyl hexyl amine and dimethylethanolamine, most preferably dimethylethanolamine.
In a preferred embodiment of the inventive method, with isocyanate-reactive component a2) and a3) and catalyzer k) insert in advance, and add the polyisocyanates a1 of the step I of the inventive method then).In this situation, temperature range preferably sets at 50 ℃-140 ℃.Catalyzer k) can with component a1), a2) or a3) each mixes, or add separately.The described reaction of step I can be carried out in non-isocyanate reactive solvents (so-called solubility promoter), does not preferably contain solubility promoter ground and carries out this reactions steps I.At component k), a1), a2) and a3) mix according to step I after, continue to stir and no longer can be detected by the IR spectrography up to the NCO group.
Subsequently, in a kind of preferred scheme, in the solubility promoter that the urethane that gained OH official can and not contained the Step II of NCO group is dissolved in volatility, can mix with water, this solubility promoter has under 1013mbar and is lower than 85 ℃ boiling point, acetone for example, for example, then with this solution and end-capping reagent a4) mix.Alternatively, at first this end-capping reagent can be mixed in the urethane of the Step II that derives from the inventive method, then the gained mixture be dissolved in this solvent.The preferred solvent content that derives from the mixture of Step II depends on its viscosity, and is 0 weight %-60 weight %, is preferably 5 weight %-30 weight % especially.Temperature is set at 0 ℃-80 ℃, is preferably 20 ℃-50 ℃.Subsequently, with polyisocyanate component a5) so be metered into, make temperature be no more than 80 ℃.Preferably in interpolation and follow-up whipping process subsequently, keep 20-60 ℃ of temperature range.Stir the mixture, no longer can be detected by the IR spectrography up to the NCO group.
In preferred embodiments, use alkali a6) to from unit a2) the acidic group of urethane carry out deprotonation wholly or in part, thereafter, water disperses.
For for disperseing in the water, under the violent stirring condition, be under the 1W/l-1000kW/l condition at stirring intensity usually, polyurethane solution is imported disperse in the water, perhaps, in this polyurethane solution of on the contrary dispersion being blunged into.Preferably water is added in the dissolved urethane.After in step VII, disperseing to finish, remove the optional volatile solvent that exists by distillation.This distillation is carried out under preferred 30-50 ℃ the temperature especially preferably under reduced pressure at 20-70 ℃.This decompression is preferably set to 50-500mbar, is preferably 100-200mbar especially.Can at first set desired temperatures and satisfy the required decompression of distillation then, perhaps conversely.In a program very particularly preferably, at first set the decompression of 100-200mbar, and then dispersion is heated to 40 ℃ from room temperature.The ratio of the solvent in the dispersion that the benefit of this mode is to make is little, and with respect to described dispersion, it is usually less than 0.5 weight %.
In addition, although be not preferred, possible is adds and can not be distilled other the solubility promoter of removing.So use these solubility promoters, make them be at most 4 weight %, preferably be at most 2 weight % with respect to dispersion with respect to the content of dispersion.Be preferably the dispersion that preparation does not contain solubility promoter especially.
Use at least a catalyzer k that is selected from tertiary amine, tin compound, zn cpds or bismuth compound) accelerate reactions steps I, be preferably triethylamine, 1 especially, 4-diazabicyclo [2.2.2] octane, two stannous octoates and dibutyl tin laurate.Very particularly preferably two stannous octoates and dibutyl tin laurate.This catalysts for polyurethanes k) formation of carbamate among the accelerating step II.In EP-A2006/005878, used above-mentioned catalyzer equally.But they more are used as the end-blocking catalyzer in the step of back in this method herein.
The aqueous dispersion of the self-crosslinking that can be obtained by the method for the invention has with respect to this dispersion 10 weight %-70 weight % solid contents, the involatile constituent of preferred 30 weight %-50 weight %, this solid content is by measuring 100 ℃ of following desciccator diaphragm to constant weights.
Can be used as the single component baking system that contains free hydroxyl group by the dispersion that method of the present invention obtains and produce paint vehicle, colorant and other preparation.In this article, also can use conventional auxiliary agent and additive in the paint-on technique in the lump, for example pigment, flow promotor (Verlaufsmittel), antifrother or catalyzer.For extra crosslinked purpose in curing, also can be the mixture with other alcohol-reactive compounds, for example amino cross-linked resin, for example, such as melamine resin and/or urea resin.
The present invention also provides the aqueous dispersion of self-crosslinking of the present invention to be used to produce the purposes of colorant, paint vehicle or tackiness agent, primes especially for automobile, and is used for jar and is coated with the purposes that applies with coiled material.
These moisture single components that comprise self-crosslinking aqueous dispersion of the present invention apply that agent can for example spray by all any means in the paint-on technique, smear, dip-coating, flow coat or use roller and scraper, are applied to arbitrarily on the resistant substrates with one or more layers.Paint film generally has the dry film thickness of 0.001-0.3mm.
The example of suitable substrate is metal, plastics, timber or glass.Paint film be solidificated in 80-260 ℃, preferably under 130-240 ℃, carry out.
This moisture single component applies agent and preferably is suitable for producing coating and enamelled coating on steel plate, for example is used to produce vehicle body, machine, baffle plate, the steel plate of drum or container.Be preferably the purposes that is used to produce vehicle paint base (Automobilf ü ller) and/or finishing paint especially.
Embodiment
Figure A20078004686500121
N 3300：
Based on the isocyanic ester of hexamethylene diisocyanate, Bayer MaterialScience AG, Leverkusen, Germany
Other chemical reagent obtains (Sigma-Aldrich ChemieGmbH, Taufkirchen, Germany) by chemical reagent special commerce merchant.
Unless dated especially, all per-cent data all by weight.
Unless dated especially, used analysis to measure all carries out at 23 ℃.
The viscosity of report be under 23 ℃ according to DIN 53019 by the rotary viscosity method of masurement, use available from Anton Paar Germany GmbH, Ostfildern, Germany, rotational viscosimeter measure.
Unless mention especially, NCO content is all by volume measured according to DIN-EN ISO 11909.
The particle size of report is that (instrument: Malvern Zetasizer 1000 MalvernInst.Limited) measures by means of laser correlation spectrometry (Laserkorrelationsspektroskopie).
Solid content is by measuring through the sample of weighing 100 ℃ of heating.Under the constant weight situation, calculate solid content by the weight of weighing sample again.
(wavelength is 2260cm by means of the IR spectrography in the detection of free NCO group -1) carry out.
Embodiment B 1): (the DMP-end-blocking in MPA/SN100 of reforming of EP-A 1311571B1 N 3300)
According to the experiment B1 among the EP-A 1311571, with 625g's
Figure A20078004686500122
N 3300, the 1-methoxy propyl yl acetate of 104g and 209g's
Figure A20078004686500123
100 (shells) are heated to 50 ℃.So add the 3 of 314g to solution, so that temperature is no more than 65 ℃.Continue down to stir at 50 ℃ then, no longer can be detected (about 1 hour) up to isocyanate groups.The viscosity of solution be 3910mPas (23 ℃, shearing rate 186s -1)
Embodiment B 2): the end capped N 3300 of (being similar to 1) solvent-free DMP-)
With 625g's
Figure A20078004686500131
N 3300 is heated to 50 ℃ in agitator.Then, so add the 3 of 314g, so that temperature is no more than 65 ℃.Continue down to stir at 65 ℃ then, no longer can be detected (about 1 hour) by the IR spectrography up to isocyanate groups.It is very sticking that this mixture promptly becomes.When being cooled to room temperature, do not show flowability, even and if after being heated to 50 ℃, can not discharge this product.
Because can't measure, this is not suitable for preparing self-crosslinkable polyurethane dispersions through end capped polyisocyanates.Therefore, preparing the corresponding dispersion that does not contain solubility promoter with the method that is similar to prior art can not realize by saving solubility promoter simply.
Embodiment B 3): import the diisopropylamine work with the method B1 among the EP 1311571B1 the samely Experiment for end-capping reagent
Repeat embodiment 1) the middle program of putting down in writing, but add the diisopropylamine of 324.3g rather than the 3 of 314g.
After the preparation at once, the viscosity of solution be 49300mPas (23 ℃, shearing rate 186s -1).Among a couple of days, form crystal in the container, and no longer show flowability.
As the result of high viscosity and crystallization tendency, can not be similar to the end capped system of dimethyl pyrazole among the EP-A 1311571, use the end capped isocyanate groups of diisopropylamine to prepare self-crosslinkable polyurethane dispersions.
Embodiment D1), non-of the present invention, reforming corresponding to the dispersion of EP-A 1311571D7
Insert the acid number that 234.8g has 3.3% OH content and about 3mgKOH/g in advance at 2 liters agitators, neopentyl glycol by 39.7%, 6.4% trimethyl propane, the polyester that 43.5% Tetra Hydro Phthalic Anhydride and 10.4% hexanodioic acid constitute, has the acid number of 2.0% OH content and about 1mg KOH/g with 234.8g, by 30.4% 1, the 6-hexylene glycol, the polyester that 16.9% neopentyl glycol and 52.7% hexanodioic acid constitute, and with the dimethylol propionic acid of this mixture together with 31.5g, 28.95g TriMethylolPropane(TMP), 69.86g N-Methyl pyrrolidone and the stannous octoate of 0.80g be heated to 130 ℃ together, and under agitation condition, homogenized 30 minutes.Then this mixture is cooled to 90 ℃ and under violent stirring, add the isophorone diisocyanate (IPDI) of 99.4g.Afterwards immediately with this mixture heating up to 130 ℃, and keep this temperature no longer can be detected by the IR spectrography up to isocyanate groups.
Then this mixture is cooled to 70 ℃ and derive from Embodiment B 1 with 200.2g) the solution through blocked polyisocyanates mix.After 30 minutes, add the N of 20.9g, the N-dimethylethanolamine in this mixture of 70 ℃ of following restir 10 minutes, and then adds the 665g deionized water.
The character of dispersion is as follows:
Solid content 49.6%
PH value 7.7
Viscosity mPas (23 ℃, shearing rate 186s -1) 343mPas
Particle size (laser correlation spectrometry, LCS) 73nm
Embodiment D2), non-of the present invention, 2006/005878 described as EP-A, based on embodiment D1, DMP-is end capped, the self-crosslinking dispersion that do not contain solubility promoter, with the catalysis of termination procedure Agent original position end-blocking
In 2 liters agitator, insert 234.8g in advance and have the acid number of 3.3% OH content and about 3mgKOH/g, neopentyl glycol by 39.7%, 6.4% trimethyl propane, the polyester that 43.5% Tetra Hydro Phthalic Anhydride and 10.4% hexanodioic acid constitute, and 234.8g has the acid number of 2.0% OH content and about 1mg KOH/g, by 30.4% 1, the 6-hexylene glycol, the polyester that 16.9% neopentyl glycol and 52.7% hexanodioic acid constitute, and this mixture is heated to 130 ℃ together with the dimethylol propionic acid of 31.5g and the TriMethylolPropane(TMP) of 28.95g, and under agitation condition, homogenized 30 minutes.Then this mixture is cooled to 90 ℃ and under violent stirring, add the isophorone diisocyanate (IPDI) of 99.4g.Afterwards immediately with this mixture heating up to 130 ℃, and keep this temperature no longer can be detected by the IR spectrography up to isocyanate groups.
Then this mixture is cooled to 70 ℃, adds the acetone of 140g afterwards and be cooled to 40 ℃.Add the 3 of 50.5g and two stannous octoates of 0.8g at 40 ℃, stirred then 20 minutes, afterwards, be metered into 102.4g's in the process at 1 hour
Figure A20078004686500141
N 3300, and the temperature of this moment is 35-40 ℃.Continue to stir and no longer can be detected up to isocyanate groups in 1 hour by the IR spectrography.The N that adds 20.9g then, the N-dimethylethanolamine continues down to stir 10 minutes at 40 ℃, and then adds the deionized water of 789g.Do not form dispersion; On the contrary, deposited coarse grained throw out immediately.Do not obtain dispersion with the further dilution of the water of 363g yet.
Embodiment D3) of the present invention, be similar to embodiment D2, DMP-is end capped, do not contain hydrotropy The self-crosslinking dispersion of agent, but before the urethane that contains the OH group forms, add catalyzer system Be equipped with
In 2 liters agitator, insert 234.8g in advance and have the acid number of 3.3% OH content and about 3mgKOH/g, neopentyl glycol by 39.7%, 6.4% trimethyl propane, the polyester that 43.5% Tetra Hydro Phthalic Anhydride and 10.4% hexanodioic acid constitute, and 234.8g has the acid number of 2.0% OH content and about 1mg KOH/g, by 30.4% 1, the 6-hexylene glycol, the polyester that 16.9% neopentyl glycol and 52.7% hexanodioic acid constitute, and with the dimethylol propionic acid of this mixture together with 31.5g, 28.95g TriMethylolPropane(TMP) and two stannous octoates of 0.8g be heated to 130 ℃ together, and under agitation condition, homogenized 30 minutes.Then this mixture is cooled to 90 ℃ and under violent stirring, add the isophorone diisocyanate (IPDI) of 99.4g.Afterwards immediately with this mixture heating up to 130 ℃, and keep this temperature no longer can be detected by the IR spectrography up to isocyanate groups.
Then this mixture is cooled to 70 ℃, adds the acetone of 140g afterwards and be cooled to 40 ℃.At 40 ℃ of 3 that add 50.5g, continue then to stir 20 minutes, afterwards, be metered into 102.4g's in the process at 1 hour N 3300, and the temperature of this moment is 35-40 ℃.Continue to stir and no longer can be detected up to isocyanate groups in 1 hour by the IR spectrography.The N that adds 20.9g then, the N-dimethylethanolamine continues down to stir 10 minutes at 40 ℃, and then adds the deionized water of 789g.Formed the dispersion of (feinteilig) in small, broken bits, by 40 ℃ in the decompression under (120mbar) distillation about 2 hours, removed acetone.
The character of dispersion is as follows:
Solid content 49.0%
PH value 8.0
Viscosity mPas (23 ℃, shearing rate 186s -1) 977mPas
Particle size (laser correlation spectrometry, LKS) 103nm
Embodiment D4) of the present invention, be similar to embodiment D3, but use different end-capping reagents: fourth Ketoxime-end capped does not contain the self-crosslinking dispersion of solubility promoter
In 2 liters agitator, insert 234.8g in advance and have the acid number of 3.3% OH content and about 3mgKOH/g, neopentyl glycol by 39.7%, 6.4% trimethyl propane, the polyester that 43.5% Tetra Hydro Phthalic Anhydride and 10.4% hexanodioic acid constitute, and 234.8g has the acid number of 2.0% OH content and about 1mg KOH/g, by 30.4% 1, the 6-hexylene glycol, the polyester that 16.9% neopentyl glycol and 52.7% hexanodioic acid constitute, and with the dimethylol propionic acid of this mixture together with 31.5g, 28.95g TriMethylolPropane(TMP) and two stannous octoates of 0.8g be heated to 130 ℃ together, and under agitation condition, homogenized 30 minutes.Then this mixture is cooled to 90 ℃ and under violent stirring, add the isophorone diisocyanate (IPDI) of 99.4g.Afterwards immediately with this mixture heating up to 130 ℃, and keep this temperature no longer can be detected by the IR spectrography up to isocyanate groups.
Then this mixture is cooled to 70 ℃, adds the acetone of 140g afterwards and be cooled to 40 ℃.At 40 ℃ of Diacetylmonoximes that add 45.7g, continue then to stir 20 minutes, afterwards, be metered into 102.4g's in the process at 1 hour
Figure A20078004686500161
N 3300, and the temperature of this moment is 35-40 ℃.Continue to stir and no longer can be detected up to isocyanate groups in 1 hour by the IR spectrography.The N that adds 20.9g then, the N-dimethylethanolamine continues down to stir 10 minutes at 40 ℃, and then adds the deionized water of 975g.Formed dispersion in small, broken bits,, reduced pressure about 2 hours of (120mbar) distillation, removed acetone by at 40 ℃.
The character of dispersion is as follows:
Solid content 43.9%
PH value 8.1
Viscosity mPas (23 ℃, shearing rate 186s -1) 387mPas
Particle size (laser correlation spectrometry, LKS) 111nm
Embodiment D5), be similar to embodiment D3, but use different end-capping reagents according to of the present invention: Diisopropylamine-end capped does not contain the self-crosslinking dispersion of solubility promoter
In 2 liters agitator, insert 234.8g in advance and have the acid number of 3.3% OH content and about 3mgKOH/g, neopentyl glycol by 39.7%, 6.4% trimethyl propane, the polyester that 43.5% Tetra Hydro Phthalic Anhydride and 10.4% hexanodioic acid constitute, and 234.8g has the acid number of 2.0% OH content and about 1mg KOH/g, by 30.4% 1, the 6-hexylene glycol, the polyester that 16.9% neopentyl glycol and 52.7% hexanodioic acid constitute, and with the dimethylol propionic acid of this mixture together with 31.5g, 28.95g TriMethylolPropane(TMP) and two stannous octoates of 0.8g be heated to 130 ℃ together, and under agitation condition, homogenized 30 minutes.Then this mixture is cooled to 90 ℃ and under violent stirring, add the isophorone diisocyanate (IPDI) of 99.4g.Afterwards immediately with this mixture heating up to 130 ℃, and keep this temperature no longer can be detected by the IR spectrography up to isocyanate groups.
Then this mixture is cooled to 70 ℃, adds the acetone of 140g afterwards and be cooled to 40 ℃.At 40 ℃ of Diacetylmonoximes that add 45.7g, continue then to stir 20 minutes, afterwards, be metered into 102.4g's in the process at 1 hour
Figure A20078004686500171
N 3300, and the temperature of this moment is 35-40 ℃.Continue to stir and no longer can be detected up to isocyanate groups in 1 hour by the IR spectrography.The N that adds 20.9g then, the N-dimethylethanolamine continues down to stir 10 minutes at 40 ℃, and then adds the deionized water of 975g.Formed dispersion in small, broken bits,, reduced pressure about 2 hours of (120mbar) distillation, removed acetone by at 40 ℃.
The character of dispersion is as follows:
Solid content 48.9%
PH value 8.2
Viscosity mPas (23 ℃, shearing rate 186s -1) 1650mPas
Particle size (laser correlation spectrometry, LKS) 113nm
The utilisation technology of dispersion of the present invention (anwendungstechnisch) performance as shown in Table 1.
Used following preparation of compositions varnish (Klarlacke).Produced film by this varnish, and at room temperature dry 10 minutes cured under 140 ℃ or 160 ℃ 30 minutes then.On utilisation technology, estimate the performance of gained film.
According to DIN's 53157
Figure A20078004686500172
Method is measured pendulum hardness.
Be exposed to following each solvent clock time postevaluation in 1 fen solvent resistance by following order
Figure A20078004686500173
: dimethylbenzene/methoxy propyl yl acetate/ethyl acetate/acetone; Estimate: 0, very good, to 5, poor.
Table 1
Derive from the dispersion of following embodiment numbering D1 (comparison) D3 D4 D5
The product weighing [g] of dispersion 150.0 150.0 150.0 150.0
Additol XW 395，[g] 1.2 1.2 1.2 1.2
10%N in water, N-dimethylethanolamine, [g] 1.8 0.7 - -
Distilled water [g] 12.0 17.0 5.0 15.0
Total amount [g] 165.0 168.9 156.2 166.2
Solid [%] 45.1 43.5 42.2 44.1
The pH value 8.3 8.3 8.3 8.3
Flowing time ISO cup 5mm[s] 37 41 30 40
Cure condition: 10min. room temperature+30min.140 ℃
Pendulum hardness [s] 21 20 14 18
Solvent resistance 1min. (0-5) 4444 4444 4444 4444
Paint film appearance (1) i.O. i.O. i.O. i.O.
Cure condition: 10min. room temperature+30min.160 ℃
Pendulum hardness [s] 21 20 18 16
Solvent resistance 1min. (0-5) 4444 4444 4444 4444
Paint film appearance (1) i.O. i.O. i.O. i.O.
(1) i.O.=is satisfied, zero defect
Dispersion by the inventive method preparation shows that membrane forms the requirement of middle expectation, and the solvent resistance of cured film and the data of pendulum hardness are also satisfactory.Shortcoming when the comparative example of containing solvent from D1 compares does not appear in the situation of dispersion of the present invention.

Claims (13)

1, be used to prepare the method for the aqueous polyurethane dispersion of self-crosslinking, this method comprises the steps:
I. allow a1) polyisocyanates and a2) and mixture a3) react,
A2) contain the anionic hydrophilic reagent of the average OH functionality of at least one isocyanate-reactive group and having 〉=1,
A3) have＞at least a polyol component of 1 average OH functionality,
A2 wherein) and mixture a3) or component a1) comprise
K) at least a catalyzer;
II. obtain the urethane that OH is functional, do not contain the NCO group from step I, this urethane subsequently with
III.a4) the reactive end-capping reagent at isocyanate groups mixes;
This mixture that IV. will derive from Step II I subsequently with
A5) one or more are selected from a1) polyisocyanates reaction, these polyisocyanates and a1) identical or different, then
V. from step IV obtain that OH is functional, the urethane that do not contain the NCO group and end-blocking the physical mixture of polyisocyanates, wherein, subsequently or
VI. by adding
A6) neutralization reagent
Acidic group to the OH functional polyurethanes carries out deprotonation wholly or in part;
The urethane that VII. also will derive from this step VI is scattered in the water
Step VII carries out before step VI.
2, the described method of claim 1, step VI carries out before step VII.
3, the described method of claim 1, step VII carries out before step VI.
4, each described method among the claim 1-3, wherein, used end-capping reagent is the compound that is selected from Diacetylmonoxime, diisopropylamine and 3 among the Step II I.
5, each described method among the claim 1-4, wherein, to derive from the urethane of Step II, use after Step II or Step II I at the most that 30 weight % are selected from the solvent or the solvent mixture of acetone, methyl ethyl ketone and tetrahydrofuran (THF) and their mixture, and after step VII, remove described solvent or solvent mixture subsequently by distillation.
6, the aqueous polyurethane dispersion of self-crosslinking, it can make by each described method among the claim 1-5.
7, the aqueous polyurethane dispersion of the described self-crosslinking of claim 6 is used to prepare the purposes that applies agent.
8, apply agent, it comprises the aqueous polyurethane dispersion of the described self-crosslinking of claim 6.
9, the described coating agent of claim 8 is selected from colorant, paint vehicle and tackiness agent.
10, the method that is used for coated substrate is wherein used claim 8 and/or 9 described coating agent.
11, the described method of claim 10 wherein, is used the parts of claim 8 and/or 9 described coating agent applying machine motor-vehicle bodies or motor vehicle body.
12, base material, it comprises coating, and described coating comprises claim 8 or 9 described coating agent.
13, the described base material of claim 12, described base material is the parts of whole motor vehicle body or motor vehicle body.
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DE102005030225A1 (en) * 2005-06-29 2007-01-04 Bayer Materialscience Ag Self-crosslinking PU dispersions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103502322A (en) * 2011-03-02 2014-01-08 陶氏环球技术有限责任公司 A coating composition and articles made therefrom
CN103502322B (en) * 2011-03-02 2016-03-02 陶氏环球技术有限责任公司 Coating composition and the goods prepared by this coating composition

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WO2008074398A1 (en) 2008-06-26
US20080161487A1 (en) 2008-07-03
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CA2672705A1 (en) 2008-06-26
EP2121787A1 (en) 2009-11-25
RU2471815C2 (en) 2013-01-10
ZA200903631B (en) 2010-07-28
HK1139165A1 (en) 2010-09-10
RU2009127498A (en) 2011-01-27
JP2010513610A (en) 2010-04-30
KR20090099532A (en) 2009-09-22
BRPI0720519A2 (en) 2014-04-01
EP2121787B1 (en) 2010-11-03
CN101589083B (en) 2012-02-01
DE502007005582D1 (en) 2010-12-16
ATE486896T1 (en) 2010-11-15

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